Water-dispersible polyester stabilized fluoroalkyl compositions

ABSTRACT

In this invention, an aqueous dispersion is provided to improve the oil and water repellency of materials. The aqueous dispersion comprises a polymer, at least one water dispersible polyester, and water; wherein the polymer comprises the repeating units from at least one fluoroalkyl monomer and optionally, at least one ethylenically unsaturated monomer. 
     This invention also provides an article coated with the aqueous dispersion.

FIELD OF THE INVENTION

This invention is related to compositions that provide oil andwater-repellancy to articles. Particularly, this invention relates to anoil and water-repellant composition comprising at least one polymer, atleast one water-dispersible polyester,,and water; wherein the polymercomprises at least one fluoroalkyl monomer. More particularly, thisinvention relates to an oil and water repellant composition comprisingat least one polymer, a polyethylene glycol polyester, and water;wherein the polymer comprises a perfluoroalkyl acrylate.

BACKGROUND OF THE INVENTION

Polymers and other compounds containing fluorinated monomers have beenused for providing oil and water repellency to textile substrates, suchas, fabrics and paper. These fluoroalkyl polymers are typically producedby emulsion polymerization utilizing either an anionic or a cationicsurfactant to stabilize the emulsion. These surfactants used to producethe fluoroalkyl polymers can cause foaming and degradation of the oiland water repellency of the fluoroalkyl polymer contained on the textilesubstrate. There is a need in the textile industry to develop an aqueousdispersion of a fluoroalkyl polymer utilizing a surfactant that does notfoam and degrade the oil and water repellency of the fluoroalkylpolymer.

Applicants provide a novel, oil and water repellent compositioncomprising at least one polymer, at least one water-dispersiblepolyester, and water that reduces foaming and degradation of the oil andwater repellency of the fluoroalkyl polymer.

BRIEF SUMMARY OF THE INVENTION

It is an object of this invention to provide an aqueous dispersion thatprovides oil and water-repellency to articles. The aqueous dispersioncomprises at least one polymer, at least one water dispersiblepolyester, and water; wherein the polymer comprises repeating units fromat least one fluoroalkyl monomer.

It is another object of this invention to provide substrates andarticles coated with the aqueous dispersion.

In accordance with one embodiment of the invention, a pre-emulsion isprovided. The pre-emulsion comprises at least one fluoroalkyl monomer,at least one water dispersible polyester, and water.

In accordance with another embodiment of the invention, a miniemulsionis provided. The mini-emulsion comprises at least one fluoroalkylmonomer, at least one water dispersible polyester, and water.

In accordance with still another embodiment of the invention, an aqueousdispersion is provided. The aqueous dispersion comprises a polymer, atleast one water dispersible polyester, and water; wherein the polymercomprises the repeating units from at least one fluoroalkyl monomer andoptionally, at least one ethylenically unsaturated monomer.

In accordance with yet another embodiment of the invention, an articlecoated with the aqueous dispersion is provided.

DETAILED DESCRIPTION

In the present invention, an aqueous dispersion is provided. The aqueousdispersion comprises a polymer, at least one water-dispersiblepolyester, and water; wherein the polymer comprises the repeating unitsfrom at least one fluoroalkyl monomer.

The fluoroalkyl monomer is a (meth)acrylate having a Rf group. The(meth)acrylate having a Rf group is a compound wherein the Rf group ispresent in the alcohol residue moiety of the (meth)acrylate. The Rfgroup is a group having at least two hydrogen atoms of an alkyl groupsubstituted by fluorine atoms.

The carbon number of the Rf group is from 2 to about 20, preferably fromabout 4 to about 16, and most preferably from 6 to 14. The Rf group ispreferably a straight chain or branched group. In the case of a branchedgroup, the branched moiety is present at the terminal portion of the Rfgroup and preferably a short chain having from 1 to 4 carbon atoms. TheRf group may contain other halogen atoms in addition to fluorine atoms.As such, chlorine atoms are preferred. Further, an etheric oxygen atommay be inserted between carbon atoms in the Rf group.

The number of fluorine atoms in the Rf group is preferably at leastabout 60%, more preferably at least 80%, as represented by [(the numberof fluorine atoms in the Rf group)/(the number of hydrogen atomscontained in an alkyl group having the same carbon number as the Rfgroup)]×100(%). Further, the Rf group is preferably a group having allof hydrogen atoms of an alkyl group substituted by fluorine atoms (i.e.a perfluoroalkyl group).

The number of carbon atoms in the perfluoroalkyl group is preferablyfrom 2 to about 20, more preferably from about 4 to about 16, and mostpreferably from 6 to 14. If the carbon number is less than 2, the waterrepellency and oil repellency of the aqueous dispersion tend to be low.If the carbon number exceeds 20, the (meth)acrylate having aperfluoroalky group tends to be solid at room temperature makinghandling difficult.

In one embodiment, the fluoroalkyl monomer is represented by Formula 1:Rf-Q-OCOCR═CH₂  (1)wherein Rf is defined as discussed previously, Q is a bivalent organicgroup, and R is a hydrogen atom or a methyl group. Q is preferably(CH₂)_(p+q)—; —(CH₂)_(p)CONH(CH₂)_(q)—; —(CH₂)_(p)OCONH(CH₂)_(q)—;—(CH₂)_(p)SO₂NR′(CH₂)_(q)—; —(CH₂)_(p)NHCONH(CH₂)_(q)— or—(CH₂)_(p)CH(OH)—(CH₂)_(q)—, wherein R′ is a hydrogen or an alkyl group,and each of p and q is an integer of at least 0, provided that p+q is aninteger of from 1 to 22. It is preferred that Q is —(CH₂)_(p+q)—;—(CH₂)_(p)CONH(CH₂)_(q)—; —(CH₂)_(p)SO₂NR′(CH₂)_(q)—; wherein q is aninteger of at least 2; and p+q is from 2 to 6. Particularly preferred is(CH₂)_(p+q), wherein p+q is from 2 to 6.

Specific examples of the (meth)acrylate having a Rf group include, butare not limited to:

F(CF₂)₅CH₂OCOCR═CH₂,

F(CF₂)₆CH₂CH₂OCOCR═CH₂,

H(CF₂)₆CH₂CH₂OCOCR═CH₂,

F(CF₂)₈CH₂CH₂OCOCR═CH₂,

i-C₃F₇(CF₂)₅CH₂CH₂OCOCR═CH₂,

F(CF₂)₈SO₂N(C₃H₇)CH₂CH₂OCOCR═CH₂,

F(CF₂)₈(CH₂)₄OCOCR═CH₂,

F(CF₂)₈SO₂N(CH₃)CH₂CH₂OCOCR═CH₂,

F(CF₂)₈SO₂N(C₂H₅)CH₂CH₂OCOCR═CH₂,

F(CF₂)₈CONHCH₂CH₂OCOCR═CH₂,

i-C₃F₇(CF₂)₅(CH₂)₃OCOCR═CH₂,

i-C₃F₇(CF₂)₅CH₂CH(OCOCH₃)OCOCR═CH₂,

i-C₃F₇(CF₂)₅CH₂CH₂CH(OH)CH₂OCOCR═CH₂,

F(CF₂)₉CH₂CH₂OCOCR═CH₂, and

F(CF₂)₉CONHCH₂CH₂OCOCR═CH₂.

In these examples, R represents a hydrogen or a methyl group, and i-C₃F₇represents a perfluoroisopropyl group [(CF₃)₂CF—].

Two or more types of fluoroalkyl monomers may be used in combination.Preferably, the fluoroalkyl monomer is selected from the groupconsisting of perfluoroalkylmethyl acrylate and perfluoroalkylethylacrylate. More preferably, the fluoroalkyl compound isperfluoroalkylethyl acrylate or perfluoroalkylmethyl acrylate; whereinthe alkyl group has about 6 to about 14 carbon atoms. Most preferably,the fluoroalkyl compound is perfluoroalkylethyl methacrylate

In another embodiment of this invention, the polymer in the aqueousdispersion comprises the repeating units from at least one fluoroalkylmonomer and from at least one ethylenically unsaturated monomer. Theethylenically unsaturated monomer is at least one acrylic or vinylmonomer known in the art capable of polymerizing with the fluoroalkylmonomer. The ethylenically unsaturated monomer can be added as a singletype of monomer or as a mixture. Examples of suitable ethylenicallyunsaturated monomers, include, but are not limited to, styreniccompounds, ethylenically unsaturated compounds, nitrogen-containingcompounds, vinyl chloride, and vinylidene chloride.

Suitable styrenic compounds include, but are not limited to, styrene,α-methyl styrene, vinyl naphthalene, vinyl toluene, chloromethylstyrene, and the like.

Ethylenically unsaturated compounds include, but are not limited to,methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate,ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexylmethacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, octylacrylate, octyl methacrylate, isodecyl acrylate, isodecyl methacrylate,lauryl methacrylate, lauryl acrylate, tridecyl acrylate, tridecylmethacrylate, stearyl acrylate, stearyl methacrylate, glycidylmethacrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate,di-octylmaleate, acetoacetoxyethyl methacrylate, acetoacetoxyethylacrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl acrylate,diacetone acrylamide, acrylamide, methacrylamide, hydroxyethylmethacrylate, hydroxyethyl acrylate, allyl methacrylate,tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexylmethacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexylmethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate,isodecyl methacrylate, isodecyl acrylate, 2-methoxy acrylate, 2-methoxymethacrylate, 2-(2-ethoxyethoxy) ethylacrylate, 2-phenoxyethyl acrylate,2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate,caprolactone acrylate, caprolactone methacrylate, polypropyleneglycolmonoacrylate, polypropyleneglycol monomethacrylate,poyethyleneglycol(400) acrylate, polypropyleneglycol(400) methacrylate,benzyl acrylate, benzyl methacrylate, sodium 1-allyloxy-2-hydroylpropylsulfonate, acrylonitrile, and the like.

Nitrogen-containing compounds include, but are not limited to,methacrylamide, t-butylaminoethyl methacrylate, dimethylaminoethylmethacrylate, diethylaminoethyl methacrylate, N,N-dimethylaminopropylmethacrylamide, 2-t-butylaminoethyl methacrylate, N,N-dimethylaminoethylacrylate, 2-acrylamido-2-methylpropanesulfonic acid,N-(2-methacryloyloxy-ethyl)ethylene urea, methacrylamidoethylethyleneurea, and the like.

Ethylenically unsaturated monomers are described in “The BrandonWorldwide Monomer Reference Guide and Sourcebook” Second Edition, 1992,Brandon Associates, Merrimack, New Hampshire; and in “Polymers andMonomers”, the 1996–1997 Catalog from Polyscience, Inc., Warrington, Pa.

Two or more of the ethylenically unsaturated monomers may be used incombination. Preferably, the ethylenically unsaturated monomer has up toabout 18 carbon atoms, such as, 2-ethylhexyl acrylate, 2-ethylhexylmethacrylate, lauryl methacrylate and stearyl methacrylate. Mostpreferably, the ethylenically unsaturated monomer is laurylmethacrylate.

The amount of fluoroalkyl monomer repeating units in the polymer rangesfrom about 50 to about 100 weight percent based on the total weight ofmonomer utilized to produce the polymer. Preferably, the amount offluoroalkyl repeating units in the polymer ranges from 60 to 80 weightpercent based on the total weight of monomer utilized to produce thepolymer.

The weight average molecular weight (Mw) of the polymer ranges fromabout 3000 to about 2,000,000, preferably 10,000 to 500,000 asdetermined by gel permeation chromatography.

The water-dispersible polyester can be any water-dispersible polyesterthat is known in the art capable of emulsifying the fluoroalkyl monomer,and optionally, the ethyleneically unsaturated monomer and stabilizingthe aqueous dispersion. The water-dispersible polyester can be either anonionic or anionic water-dispersible polyester. Examples ofwater-dispersible polyesters sold by Eastman Chemical Company includeLUBRIL QC, LUBRIL QCX, LUBRIL QCF, LUBRIL QCJ, VELVETOL 1471, andVELVETOL 251C. Other water-dispersible polyesters include MILEASE T,MILEASE HPA, HILEASE NUVA, and AFILAN 8228 sold by Clariant, andASTRAPLUSH and TANAPAL ACF sold by Bayer. Preferably, thewater-dispersible polyester is nonionic. Polyethylene glycol polyesteris the preferred water-dispersible polyester. Polyethylene glycolpolyester is available from Eastman Chemical Company as LUBRIL QC. Theamount of water-dispersible polyester solids in the aqueous dispersionranges from about 1% to about 20% based on the total weight of theaqueous dispersion, preferably from about 1% to about 5%, and mostpreferably 3% to 5%.

The aqueous dispersion may be prepared by any polymerization methodknown in the art. In one embodiment, a process to produce an aqueousdispersion is provided. The process comprises: 1) contacting at leastone fluoroalkyl monomer, at least one water-dispersible polyester,water, and optionally an ethylenically unsaturated monomer to produce amixture; and 2) polymerizing the mixture to produce the aqueousdispersion.

Preferably, the aqueous dispersion is prepared by using emulsionpolymerization techniques. The polymer may, as is known in the art, beprepared using free radical emulsion polymerization techniques thatyield structured or unstructured particles. Structured particlesinclude, for example, core/shell particles, raspberry particles,.andgradient particles. The process is carried out in an emulsionpolymerization zone comprising at least one reactor in the presence ofan initiator. Generally, the reactor is fitted with a stirrer andexternal means for either heating or cooling the charge. Thepolymerization temperature is not particularly limited to a certainvalue, but is preferably from about 20° C. to about 155° C., and mostpreferably from 40° C to 85° C.

Any initiator known in the art for emulsion polymerization can beutilized. Typical initiators include, but are not limited to, hydrogenperoxide, potassium or ammonium peroxydisulfate, dibenzoyl peroxide,lauryl peroxide, ditertiary butyl peroxide, ammonium persulfate, alkalipersulfuate, 2,2′-azobisisobutyronitrile, t-butyl hydroperoxide, benzoylperoxide, dicetyl peroxydicarbonate, tertiarybutylperoxy neodecanoate,tertiarybutylperoxy benzoate, cumene hydroperoxide, dicumylperoxide,di-benzoyl peroxide, 2,2′azobis(2-aminopropane)dihydrochloride,2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride and the like.Preferably, the initiator is 2,2′azobis(2-aminopropane)dihydrochloride.The amount of initiator utilized in the polymerization process is thatwhich is sufficient to polymerize the fluoroalkyl monomer andoptionally, the ethylenically unsaturated monomer. Preferably, theamount of initiator ranges from about 0.2 to about 1% by weight based onthe total amount of monomer, most preferably, 0.1 to 0.2% by weight.

One advantage of this inventive process is that water-soluble organicsolvents are not necessary to improve the emulsifiability, therefore,the aqueous dispersion has less volatile organic compound content thanother fluoroalkyl aqueous dispersions utilizing solvents. However,water-soluble organic solvents can be used to produce the inventiveaqueous dispersions. Examples of water-soluble organic solvents include,but are not limited to, acetone, methyl ethyl ketone, ethyl acetate,propylene glycol, dipropylene glycol, tripropylene glycol, ethanol andthe like. The water-soluble organic solvent is usually used in theamount of not more than about 30 parts by weight, preferably from 5 to20 parts by weight, based on 100 parts by weight of the total amount ofmonomer.

Reducing agents, catalysts, chain transfer agents, crosslinking agents,reactive surfactants, and water-dispersible/water-soluble polymers knownin the art may be used to prepare the polymer. The sequence of additionof these compounds can vary, and these compounds can be added to thepolymerization process at varying times.

Suitable reducing agents are those that increase the rate ofpolymerization and include for example, sodium sulfite, sodiumbisulfite, sodium metabisulfite, sodium hydrosulfite, sodiumformaldehyde sulfoxylate, sodium thiosulfate, ascorbic acid, isoascorbicacid, and mixtures thereof. The amount of reducing agent ranges fromabout 0.1% to about 2% based on the total weight of the monomers,preferably from 0.1% to 0.3% based on the total weight of the monomers.

Polymerization catalysts are those compounds which increase the rate ofpolymerization and which, in combination with the previously describedreducing agents, may promote decomposition of the initiator underreaction conditions. Suitable catalysts include, but are not limited to,transition metal compounds such as, for example, ferrous sulfateheptahydrate, chelated forms of ferrous sulfate heptahydrate, ferrouschloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltoussulfate, and mixtures thereof. Generally, the amount of catalyst rangesfrom about 0.0001% to about 0.05% based on the total weight of themonomers, preferably from 0.001% to 0.01%.

Any chain transfer agent known in the art may be utilized that iscapable of controlling the molecular weight of the polymer. Exemplarychain transfer agents include, but are not limited to, butyl mercaptan,mercaptopropionic acid, 2-ethylhexyl 3-mercaptopropionate, n-butyl3-mercaptopropionate, octyl mercaptan, N-dodecyl mercaptan, isodecylmercaptan, octadecyl mercaptan, mercaptoacetic acid, allylmercaptopropionate, allyl mercaptoacetate, crotyl mercaptopropionate,crotyl mercaptoacetate, carbon tetrabromide, bromoform,bromotrichloromethane, sodium hypophosphite and the reactive chaintransfer agents taught in U.S. Pat. No. 5,247,040, incorporated hereinby reference. In particular, N-dodecyl mercaptan represents a preferredchain transfer agent. Generally, the amount of the chain transfer agentadded ranges from about 0.1 to about 1% by weight based on the totalamount of monomer, preferably from 0.1 to 0.3% by weight.

Crosslinking agents can be any compounds that are known in the art andcan be used to impart improved crosslinking, latex stability andsubstantivity to the polymer. The crosslinking agents can be external orinternal crosslinking agents. External-crosslinking agents causecrosslinking during drying or curing of a polymer while internalcrosslinking agents cause crosslinking to occur during polymerization.

Suitable external crosslinking agents include, but are not limited to,poly(oxyethylene) (meth)acrylates, N-methylol acrylamide or N-methylolmethacrylamide, N-butoxymethyl acrylamide, hydroxylethyl(meth) acrylate,2-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,3-chloro-2-hydroxypropyl (meth)acrylate, and glycidyl (meth)acrylate. Anexample of poly(oxyethylene) (meth)acrylates include polyethylene glycolmethacrylate. The amount of external crosslinking agent can range fromabout 0.1 to about 5% by weight based on the total amount of monomer,preferably from 2 to 3% by weight based on the total amount of monomer.

Suitable examples of internal crosslinking agents include, but are notlimited to, diallylmaleate, divinylbenzene, triethyleneglycoldimethacrylate, ethyleneglycol dimethacrylate, 1,3 butyleneglycoldiacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate,neopentyl glycol diacrylate, polyethylene glycol (600) dimethacrylate,polyethylene glycol (200) diacrylate, ethoxylated bisphenol Adiacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate,trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylatedtrimethylolpropane triacrylate, propoxylated trimethylolpropanetriacrylate, propoxylated glyceryl triacrylate, pentaerythritoltetraacrylate, and ethoxylated pentaerythritol tetraacrylate. The amountof the internal crosslinking agents can range from about 0.1 to about 5%by weight based on the total amount of monomer, preferably from 1 to 2%by weight based on the total amount of monomer.

In the preparation of the aqueous dispersion, fluoroalkyl monomers, suchas described previously, can be reacted with at least onenon-self-polymerizable, surface-active vinyl monomer (also known as anon-self-polymerizable ethylenically-unsaturated surfactant or areactive surfactant). Non-self-polymerizable, surface-active vinylmonomers will hereinafter be referred to as a reactive surfactant. Thereactive surfactant, rather than polymerizing to form a separatepolymeric surfactant, is substantially (preferably completely)incorporated into the polymer of the invention. Thus, the reactivesurfactant becomes part of the polymer. Reactive surfactants possessing,for example, isopropenylphenyl or allyl groups are preferred. Examplesinclude reactive surfactants sold by PPG Industries, Inc., as MAZON® SAM181, 183, 184, 211 surfactants which are anionic sulfates or sulfonatesand MAZON® SAM 185–187 surfactants which are nonionic surfactants. Otherreactive surfactants include the macro monomers sold by Daiichi KogyoSeiyaku under the names NIOGEN RN, AQUARON or HITENOL surfactants. Theseinclude polyoxyethylene alkyl phenyl ether compounds of the generalformulae (2), (3), and (4):

In Formulae (2), (3), and (4), R is nonyl or octyl, and n and m arepreferably integers of from 15 to 50 and 15 to 40, respectively. Morepreferably, n ranges from 20 to 40, and m from 15 to 25. HITENOL RN,HITENOL HS-20 and HITENOL A-10 products are particularly preferredreactive surfactants. Other such reactive surfactants include the sodiumalkyl allyl sulfosuccinate sold by Henkel, under the trade name TREMLF40 surfactant.

Water-dispersible and water-soluble polymers may also be employed assurfactants/stabilizers in the aqueous dispersion of the invention.Examples of such polymeric stabilizers include water-dispersiblepolyurethanes as described in U.S. Pat. Nos. 4,927,876 and 5,137,961;and alkali-soluble acrylic resins as described in U.S. Pat. No.4,839,413; both of which are herein incorporated by reference.

In one embodiment of this invention, the aqueous dispersion is producedby a process comprising: 1) contacting at least one fluoroalkyl monomer,at least one water-dispersible polyester, water and optionally, at leastone ethylenically unsaturated monomer to form an pre-emulsion; and 2)polymerizing the pre-emulsion in a emulsion polymerization zone underemulsion polymerization conditions to produce the aqueous dispersion.The emulsion polymerization zone comprises at least one reactor.

The fluoroalkyl monomer, ethylenically unsaturated monomer, polyester,and initiator can be contacted in the emulsion polymerization zone inany order. The pre-emulsion can be charged all at once (one shot method)to the emulsion polymerization zone, or the pre-emulsion can be chargedgradually over time to the emulsion polymerization zone (gradualaddition method). In the gradual addition method, pre-emulsion andinitiator are charged to the emulsion polymerization zone over a periodof time ranging from about 1 to about 10 hours, preferably, from about 2to 8 hours. The initiator can be added similarly either by a one shotmethod or gradual addition method.

In another embodiment, the aqueous dispersion can be produced by aprocess comprising: 1) contacting at least one fluoroalkyl monomer, atleast one water-dispersible polyester,,water, and optionally, at leastone ethylenically unsaturated monomer to form a pre-emulsion; 2)shearing the pre-emulsion to produce a miniemulsion; and 3) polymerizingthe miniemulsion in an emulsion polymerization zone under emulsionpolymerization conditions to produce the aqueous dispersion.

Shearing of the pre-emulsion produces the mini-emulsion. The shearingcan be conducted by any means known in the art. Generally, shearing canbe achieved using a high shearing device to form droplets ranging insize from about 50 to about 1000 nanometers to form the mini-emulsion.An example of a high shearing device is a homogenizer.

The miniemulsion can be charged all at once (one shot method) to theemulsion polymerization zone, or the miniemulsion can be chargedgradually over time to the emulsion polymerization zone (gradualaddition method). In the gradual addition method, miniemulsion andinitiator are charged to the emulsion polymerization zone over a periodof time ranging from about 1 to about 10 hours, preferably, from about 2to 8 hours. The initiator can be added similarly either by a one shotmethod or gradual addition method.

The mini-emulsion, as described above, may also be polymerized asdescribed in U.S. Pat. No. 5,686,518 and Wang et al., “Emulsion andMiniemulsion Copolymerization of Acrylic Monomers in the Presence ofAlkyd Resin,” Journal of Applied Polymer Science, Vol. 60, pp. 2069–2076(1996), each of which is incorporated in its entirety by reference.

In another embodiment of this invention, a process to produce an aqueousdispersion is provided. The process comprises:

-   -   1) contacting at least one fluoroalkyl monomer, at least one        ethylenically unsaturated monomer having up to 18 carbon atoms,        water, at least one water-dispersible polyester, at least one        internal crosslinking agent, at least one external crosslinking        agent, at least one reactive surfactant, and at least one chain        transfer agent to produce a pre-emulsion;    -   2) shearing the pre-emulsion to produce a mini-emulsion;    -   3) adding the pre-emulsion to an emulsion polymerization        reactor;    -   4) contacting at least one water-dispersible polyester with        water to produce a polyester/water mixture and routing the        polyester/water mixture to the emulsion polymerization reactor;    -   5) contacting at least one initiator and water to produce an        initiator solution and routing the initiator solution to the        emulsion polymerization reactor to produce a reaction mixture;        and    -   6) polymerizing said reaction mixture to produce the aqueous        dispersion.

In another embodiment of this invention, a process is provided toproduce an aqueous dispersion. The process comprises:

-   -   1) contacting a mixed fluoroacrylate monomer stream, lauryl        methacrylate, water, polyethylene glycol polyester, n-methyol        acrylamide, and polyoxyethylene alkyl propenylphenyl ether        sulfate to produce a pre-emulsion; wherein the mixed        fluoroacrylate monomer stream comprises 2-(perfluoroalkyl)ethyl        acrylate    -   2) shearing the pre-emulsion to produce a mini-emulsion;    -   3) adding the pre-emulsion to an emulsion polymerization        reactor;    -   4) contacting a polyethylene glycol polyester dispersion with        water to produce a polyester/water mixture and routing the        polyester/water mixture to the emulsion polymerization reactor;    -   5) contacting at least one initiator and water to produce an        initiator solution and routing the initiator solution to the        emulsion polymerization reactor to produce a reaction mixture;        and    -   6) polymerizing the reaction mixture to produce the aqueous        dispersion.

In still another embodiment of this invention, a process to produce anaqueous dispersion is provided. The process comprises:

-   -   1) contacting at least one fluoroalkyl monomer, at least one        ethylenically unsaturated monomer having up to 18 carbon atoms,        water, at least one water-dispersible polyester, at least one        internal crosslinking agent, at least one external crosslinking        agent, at least one reactive surfactant, and at least one chain        transfer agent to produce a pre-emulsion;    -   2) shearing the pre-emulsion to produce a mini-emulsion;    -   3) contacting at least one water-dispersible polyester with        water to produce a polyester/water mixture and routing the        polyester/water mixture to an emulsion polymerization reactor;    -   4) contacting at least one initiator and water to produce an        initiator solution;    -   5) adding a portion of said initiator feed to the emulsion        polymerization reactor; and    -   6) charging the miniemulsion and initiator solution to the        emulsion polymerization reactor over a period of about 1 to        about 10 hours under polymerization conditions to produce the        aqueous dispersion.

In yet another embodiment of this invention, a process to produce anaqueous dispersion is provided. The process comprises:

-   -   1) contacting a mixed fluoroacrylate monomer stream, lauryl        methacrylate, water, polyethylene glycol polyester, n-methyol        acrylamide, diallylmaleate, n-dodecylmercaptan, and        polyoxyethylene alkyl propenylphenyl ether sulfate to produce a        pre-emulsion; wherein the mixed fluoroacrylate monomer stream        comprises 2-(perfluoroalkyl)ethyl acrylate    -   2) shearing the pre-emulsion to produce a mini-emulsion;    -   3) contacting a polyethylene glycol polyester dispersion with        water to produce a polyester/water mixture and routing the        polyester/water mixture to an emulsion polymerization reactor;    -   4) contacting at least one initiator and water to produce an        initiator solution;    -   5) adding a portion of said initiator feed to the emulsion        polymerization reactor; and    -   6) charging the miniemulsion and initiator solution to the        emulsion polymerization reactor over a period of about 1 to        about 10 hours under polymerization conditions to produce the        aqueous dispersion.

The aqueous dispersion of this invention generally has a polymerconcentration ranging from about 10% to about 50% based on the weight ofthe aqueous dispersion, preferably 20% to 30%. The aqueous dispersionobtained by this invention may be used by itself as it is obtained fromthe emulsion polymerization zone or it can be purified to remove, forexample, unreacted monomers. Further, the composition of the aqueousdispersion may be adjusted by adding a surfactant or by diluting withwater or an aqueous medium. In addition, various additives can be addedto the aqueous dispersion after it is produced. Such additives include,but are not limited to, other water repellents and oil repellents,anti-fungus agents, flame retardants, antistatic agents, crease-proofingagents, antimigrants, deformers, binders, and other antifouling agents.

In another embodiment of this invention, an acid-generating compound isadded to the aqueous dispersion to produce an acid-treated aqueousdispersion. The acid-generating compound can be any that is known in theart. Examples of the acid-generating compound include, but are notlimited to, sulfuric acid, hydrochloric acid, phosphoric acid,phosphorous acid, acetic acid, hydroxy acetic acid, citric acid,sulfonic acid and their respective salts formed by ammonia, amines,aminoalcohols, and alkali metal and alkaline earth metal hydroxides.Sulfonic acids include alkyl sulfonic acids and aromatic sulfonic acids.Most preferably, para-toulene sulfonic acid is used.

The acid-generating compound can be added prior to, during, or afterpolymerization. Generally, the amount of the acid-generating compound isthat which is sufficient to improve the oil and water repellency of asubstrate contacted with the acid-treated aqueous dispersion whencompared to an aqueous dispersion not treated with the acid-generatingcompound. Preferably, the amount of the acid-generating compound addedto the aqueous dispersion ranges from about 0.01% by weight to about0.4% by weight based on the weight of the aqueous dispersion, preferably0.1% to 0.2% by weight.

The aqueous dispersion or the acid-treated aqueous dispersion of thepresent invention is applied by a method of coating on the surface of asubstrate to be treated according to a known process such as dipcoating, followed by drying or a method of spraying a treating liquid bya spray.

The substrate to be treated with the aqueous dispersion or acid-treatedaqueous dispersion of the present invention may be any textile or papermaterial and is not specifically limited. Examples of the textileinclude, but are not limited to, animal- or vegetable-origin naturalfibers such as cotton, hemp, wool, silk, etc.; synthetic fibers such aspolyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinylchloride, polypropylene, etc.; semisynthetic fibers such as rayon,acetate, etc.; and a mixture of these fibers. The textile may be in anyform such as a fiber, a yarn, a fabric and the like. When the textile isa carpet, the carpet may be formed from fibers or yarns treated with theaqueous dispersion or acid-treated aqueous dispersion of the presentinvention. Alternatively, the carpet itself may be treated with theaqueous dispersion or acid-treated aqueous dispersion of the presentinvention.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated.

EXAMPLES Example 1 Production of the Inventive Aqueous Dispersion—OneShot Addition of Miniemulsion and Initiator Solution

The components and the order of addition are summarized in Table 1.

TABLE 1 Component Amount Number Component Type (wt %) 1 Deionized WaterWater 27.61 2 Lubril QC¹ Polyester 12.38 3 n-Methylol Cross-Linking 0.70Acrylamide² Agent 4 Hitenol BC 20/20%³ Reactive 1.02 Surfactant 5 LaurylMethacrylate Acrylic 6.50 monomer 6 Perfluoro(C₆–C₁₄) Fluoroalkyl 9.73ethylacrylate⁴ Monomer 7 Wako VA-044⁵ Initiator 0.586 8 Deionized WaterWater 0.54 9 Lubril QC Initiator 0 10 Deionized Water Water 41.2 ¹LubrilQC is a polyethylene glycol polyester dispersion obtained from EastmanChemical Company. ²N-methylol acrylamide −45% by weight active solutionof N-methylol acrylamide. ³Hitenol BC 20/20% is a 20% solids solution ofHitenol BC 20 which is a polyoxyethylene alkylpropenylphenyl ethersulfate obtained from Dai-Ichi Kogyo Seiyaku Co., Ltd. of Japan.⁴Perfluoro(C₆–C₁₄)ethylacrylate typically has by weight ≦15% C₆, ≧45%C₈, ≦30% C₁₀, ≦10% C₁₂, and ≦5% C₁₄. ⁵Wako VA-044 is2,2′-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride with CAS#27776-21-2 and was obtained from Wako Chemicals USA, Inc.

Components 1–6 were charged to a 1400 mL beaker to produce apre-emulsion. The beaker was heated to 140° F. to 150° F. and stirreduniformly for 5 minutes. The pre-emulsion was routed two times through aMicrofluidics homogenizer to produce a miniemulsion having a particlesize of less than 300 nm. The miniemulsion was added to a reactionflask.

Components 9 and 10 (polyester and deionized water) were charged to areaction flask. Nitrogen purge was started, and the contents of theflask were heated to 140 to 150° F. The reaction flash was set up forreflux.

Components 7 and 8 (initiator and water) were mixed to produce aninitiator solution, and the initiator solution was added to the reactionflask. The temperature of the reaction flask was held at 140° F. to 150°F. for 6 hours. The reaction flask was cooled to 100° F., and thenitrogen purge turned off. The aqueous dispersion was recovered from thereaction flask and filtered.

Example 2 Production of the Inventive Acid-Treated AqueousDispersion—Gradual Addition of Miniemulsion and Initiator Solution

A 1500 milliliter resin flask was set up with reflux and one side feed.Nitrogen purge was started from the bottom of the resin flask.

The components and the order of addition are summarized in Table 2.

TABLE 2 Component Amount Number Component Type (wt %) 1 Deionized WaterWater 27.47 2 Lubril QC¹ Polyester 11.12 3 n-Methylol Acrylamide²Cross-Linking 0.70 Agent 4 Hitenol BC 20/20%³ Reactive 1.02 Surfactant 5Lauryl Methacrylate Acrylic monomer 6.47 6 Diallylmaleate Internalcross- 0.31 linker 7 n-Dodecylmercaptan Chain Transfer 0.03 Agent 8Perfluoro(C₆–C₁₄) Fluoroalkyl 9.65 ethylacrylate⁴ Monomer 9 Wako V-50⁵Initiator 0.007 10 Deionized Water Water 0.83 11 Wako V-50 Initiator0.014 12 Deionized Water Water 23.21 13 Deionized Water Water 16.61 14Lubril QC Polyester 1.19 15 Wako V-50 Initiator 0.01 16 Deionized WaterWater 0.83 17 Para-toluene Sulfonic Acid-Generating 0.26 Acid Compound18 Deionized Water Water 0.26 ¹Lubril QC is a polyethylene glycolpolyester dispersion obtained from Eastman Chemical Company. ²N-methylolacrylamide −48% by weight active solution of N-methylol acrylamide.³Hitenol BC 20/20% is a 20% solids solution of Hitenol BC 20 which is apolyoxyethylene alkylpropenylphenyl ether sulfate obtained from Dai-IchiKogyo Seiyaku Co., Ltd. of Japan. ⁴Perfluoro(C₆–C₁₄)ethylacrylatetypically has by weight ≦15% C₆, ≧45% C₈, ≦30% C₁₀, ≦10% C₁₂, and ≦5%C_(14.) ⁵Wako V-50 is 2,2′-azobis(2-aminopropane)dihydrochloride withCAS # 2997-92-4 and was obtained from Wako Chemicals USA, Inc.

Components 1–8 were charged to a 1400 mL beaker to produce apre-emulsion. The beaker was heated to 150° F. to 160° F. and stirreduniformly for 5 minutes. The pre-emulsion was routed four times througha Microfluidics homogenizer to produce a miniemulsion having a particlesize of less than 300 nm.

Components 13 and 14 (deionized water and water dispersible polyester)were charged to the resin flask. Medium agitation was started, and theflask was heated to a temperature in a range of 140° F. to 150° F.

Components 11 and 12 (initiator and deionized water) were mixed toproduce an initiator solution and charged to the side feed. Nitrogenpurge was started, and the contents of the flask were heated to 140 to150° F.

Components 9 and 10 (initiator and deionized water) were mixed togetherand added to the flask.

The miniemulsion and initiator solution were charged separately to theflask over a 4 hour period. After the miniemulsion and initiatorsolution were added, components 15 and 16 (initiator and deionizedwater) were mixed together and added to the flask. The temperature washeld for one hour to complete the polymerization producing an aqueousdispersion. The flask was then cooled to 100° F. or below. The nitrogenpurge was ended, and the flask was stirred for another 10 minutes priorto recovering the aqueous dispersion.

Components 17 and 18 (acid-generating compound and water) were mixedtogether and added to the aqueous dispersion to produce the acid-treatedaqueous dispersion.

Example 3 Foaming Evaluation

A 1.0% by weight aqueous dispersion of the various fluorocarboncompositions in Table 3 was made. 50 milliliters of the dispersion werepoured into a 200 millilter graduated cylinder. A stopper was placed inthe graduated cylinder, and the cylinder was inverted 20 times. Thelevel of foam in milliliters was measured from the original level ofaqueous dispersion in the graduated cylinder. The data are tabulated inTable 3.

TABLE 3 Examples # Fluorocarbon Composition Foam (ml) Inventive 3.1Acid-Treated Aqueous 11 Dispersion Inventive 3.2 Acid-Treated Aqueous 10Dispersion Comparative 3.1 APG-705² 14 Comparative 3.2 APG-5264² 14Comparative 3.3 APG-10² 16 Comparative 3.4 APG-14² 11 Comparative 3.5APG 5233² 24 Comparative 3.6 Repearl F 84³ 21 Comparative 3.7 Repearl F8025³ 19 Comparative 3.8 Zonyl 5410⁴ 14 Comparative 3.9 Zonyl 8412⁴ 15¹Inventive acid-treated aqueous dispersions. ²Fluoroalkyl dispersionobtained from Advanced Polymer, Incorporated. ³Fluoroalkyl dispersionobtained from Mitsubishi International. ⁴Fluoroalkyl dispersion obtainedfrom Dupont.From the above data, it is clearly shown that the inventive acid-treatedaqueous dispersion reduced foaming over the comparative fluorocarbondispersions.

Example 4 Oil and Alcohol Repellency

The components contained in Table 4 were mixed together to produce anoil and water-repellent composition. Different fluorocarbon dispersionsas shown in Table 5 were utilized to produce varying oil and waterrepellent compositions. Each oil and water-repellent composition wasthen padded on 100% polyester terephthalate stitchbonded fabric at 40psig to produce a coated fabric. The coated fabric was then dried for 3minutes at 350° F. to produce a cured, coated fabric. The cured, coatedfabric was then tested for repellency according to the AmericanAssociation of Textile Chemist and Colorists (AATCC) Technical ManualMethod 118-2002.

To summarize the method, the cured, coated fabric was laid on a flatsurface. A pipette was used to place 3 single drops of specified alkaneor alcohol/water solution on the surface of the cured, coated fabric.After 30 seconds, the appearance of the drops was rated to a photoscale. The ratings are associated with the, particular alkane oralcohol/water solution in question.

TABLE 4 Component Amount (wt %) ABCO Builder T-37¹ 30.0 Water 66.5Polyacrylamide Antimigrant 2.0 Mineral Oil Defoamer 0.5 FluorocarbonDispersion (20% by wt. 1.0 Solids) ¹Acrylic binder having a Tg = 37° C.obtained from Eastman Chemical Company.

TABLE 5 Isopropanol/ Fluorocarbon Water (w/w) n- n- Drakeol Example #Dispersion Isopropanol (90/10) heptane decane #34² Inventive 5.1 Acid-Pass (A)³ Fail (C)⁵ Pass (A) Pass (A) Treated Aqueous DispersionComparative Zonyl 8412 Pass (B)⁴ Fail (D) Pass (B) Pass (A) 5.1Comparative APG-705 Fails (D)⁶ Fail (D) Fail (D) Fail (C) Pass (A) 5.2Comparative APG-5233 Fail (D) Fail (D) Fail (D) Fail (D) Fail (C) 5.3Comparative APG-5264 Fail (D) Fail (D) Fail (D) Fail (D) Fail (C) 5.4Comparative Boehme Pass (A) Fail (D) Fail (D) Pass (A) 5.5 FC 4000¹¹Boehme FC 4000 was obtained from Boehme Filatex, Inc. ²Drakeol #34 is ahigh molecular alkane obtained from Penreco. ³Passes (A) means theliquid forms a clear well-rounded drop. ⁴Passes (B) means a borderlinepass; rounding drop with partial darkening. ⁵Fails (C) means wickingapparent and/or complete wetting. ⁶Fails (D) means complete wetting.

From these data, it is shown that the inventive acid-treated aqueousdispersion had superior performance over the comparative examples andfailed only to repel n-heptane. Comparative example 5.1 passed therepellency test for Drakeol #34, however, it had a borderline pass forrepellency of isopropanol and n-decane and had complete wetting of thefabric for n-heptane. The fluorocarbon compounds in comparative examples5.2–5.4 failed across the board in the repellency tests exceptcomparative 5.2 was able to repel the Drakeol #34 compound. Incomparative example 5.5, the fluorocarbon dispersion passed therepellency test for Isopropanol (90/10) and Drakeol #34, but it hadcomplete wetting in the repellency of n-heptane and n-decane.

1. A pre-emulsion comprising at least one fluoroalkyl monomer, at leastone water-dispersible polyester, water and optionally an ethylenicallyunsaturated monomer; wherein the fluoroalkyl monomer is represented bythe formula: Rf-Q-OCOCR═CH₂; wherein Q is a bivalent organic group, andR is hydrogen atom or methyl group; wherein Q is selected from the groupconsisting of —(CH₂)_(p+q)—; —(CH₂)_(p)CONH(CH₂)_(q)—;—(CH₂)_(p)OCONH(CH₂)_(q)—; —(CH₂)_(p)SO₂NR′(CH₂)_(q)—;—(CH₂)_(p)NHCONH(CH₂)_(q)—; or —(CH₂)_(p)CHOH—(CH₂)_(q)—; wherein R′ isa hydrogen or an alkyl group, and each of p and q is an integer of atleast 0, provided that p+q is an integer of from 1 to
 22. 2. Apre-emulsion according to claim 1 wherein said fluoroalkyl monomer isselected from the group consisting of: F(CF₂)₅CH₂OCOCR═CH₂,F(CF₂)₆CH₂CH₂OCOCR═CH₂, H(CF₂)₆CH₂CH₂OCOCR═CH₂, F(CF₂)₈CH₂CH₂OCOCR═CH₂,i-C₃F₇(CF₂)₅CH₂CH₂OCOCR═CH₂, F(CF₂)₈SO₂N(C₃H₇)CH₂CH₂OCOCR═CH₂,F(CF₂)₈(CH₂)₄OCOCR═CH₂, F(CF₂)₈SO₂N(CH₃)CH₂CH₂OCOCR═CH₂,F(CF₂)₈SO₂N(C₂H₅)CH₂CH₂OCOCR═CH₂, F(CF₂)₈CONHCH₂CH₂OCOCR═CH₂,i-C₃F₇(CF₂)₅(CH₂)₃OCOCR═CH₂, i-C₃F₇(CF₂)₅CH₂CH(OCOCH₃)OCOCR═CH₂,i-C₃F₇(CF₂)₅CH₂CH₂CH(OH)CH₂OCOCR═CH₂, F(CF₂)₉CH₂CH₂OCOCR═CH₂, andF(CF₂)₉CONHCH₂CH₂OCOCR═CH₂; wherein R represents a hydrogen or a methylgroup, and i-C₃F₇ represents a perfluoroisopropyl group [(CF₃)₂CF—]. 3.A pre-emulsion according to claim 1 wherein said fluoroalkyl compound isperfluoroalkylethyl acrylate or perfluoroalkylmethyl acrylate; whereinthe alkyl group has about 6 to about 14 carbon atoms.
 4. A pre-emulsionaccording to claim 1 wherein said ethylenically unsaturated monomer isat least one selected from the group consisting of styrenic compounds,ethylenically unsaturated compounds, nitrogen-containing compounds,vinyl chloride, and vinylidene chloride.
 5. A pre-emulsion according toclaim 4 wherein said styrenic compound is at least one selected from thegroup consisting of styrene, α-methyl styrene, vinyl naphthalene, vinyltoluene, and chloromethyl styrene.
 6. A pre-emulsion according to claim4 wherein said ethylenically unsaturated compounds is at least oneselected from the group consisting of methyl acrylate, acrylic acid,methacrylic acid, methyl methacrylate, ethyl acrylate, ethylmethacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate,isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate ethylhexylacrylate, ethylhexyl methacrylate, octyl acrylate, octyl methacrylate,isodecyl acrylate, isodecyl methacrylate, lauryl methacrylate, laurylacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate,stearyl methacrylate glycidyl methacrylate, alkyl crotonates, vinylacetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethylmethacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropylmethacrylate, acetoacetopropryl acrylate, diacetone acrylamide,acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethylacrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate,tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexylacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethylacrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecylacrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy)ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate,isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate,caprolactone methacrylate, polypropyleneglycol monoacrylate,polypropyleneglycol monomethacrylate, poyethyleneglycol(400) acrylate,polypropyleneglycol(400) methacrylate, benzyl acrylate, benzylmethacrylate, sodium 1-allyloxy-2-hydroylpropyl sulfonate, andacrylonitrile.
 7. A pre-emulsion according to claim 4 wherein saidnitrogen containing compounds is at least one selected from the groupconsisting of Nitrogen-containing compounds include, but are not limitedto, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate,diethylaminoethyl methacrylate, N,N-dimethylaminopropyl ethacrylamided,methacrylamide, t-butylaminoethyl methacrylate, dimethylaminoethylmethacrylate, diethylaminoethyl methacrylated, N,N-dimethylaminopropylmethylcrylamide, 2-t-butylaminoethyl methacrylate,N,N-dimethylaminoethyl acrylate, 2-acrylamido-2-methylpropanesulfonicacid, N-(2-methacryloyloxy-ethyl)ethylene urea,methacrylamidoethylethylene urea.
 8. A pre-emulsion according to claim 6wherein said ethylenically unsaturated monomer is lauryl methacrylate.9. A pre-emulsion according to claim 1 wherein said water-dispersiblepolyester is a polyethylene glycol polyester.
 10. A miniemulsioncomprising at least one fluoroalkyl monomer, at least onewater-dispersible polyester, water, and optionally an ethylenicallyunsaturated monomer; wherein the fluoroalkyl monomer is represented bythe formula: Rf-Q-OCOCR═CH₂; wherein Q is a bivalent organic group, andR is a hydrogen atom or methyl group; wherein Q is selected from thegroup consisting of —(CH₂)_(p+q)—; —(CH₂)_(p)CONH(CH₂)_(q)—;—(CH₂)_(p)OCONH(CH₂)_(q)—; —(CH₂)_(p)SO₂NR′(CH₂)_(q)—;—(CH₂)_(p)NHCONH(CH₂)_(q)—; or —(CH₂)_(p)CHOH—(CH₂ _(q)—; wherein R′ isa hydrogen or an alkyl group, and each of p and q is an integer of atleast 0, provided that p+q is an integer of from 1 to
 22. 11. Aminiemulsion according to claim 10 wherein Q is selected from the groupconsisting of —(CH₂)_(p+q)—; —(CH₂)_(p)CONH(CH₂)_(q)—;—(CH₂)_(p)OCONH(CH₂)_(q)—; —(CH₂)_(p) SO₂NR′(CH₂)_(q)—;—(CH₂)_(p)NHCONH(CH₂)_(q)—; or —(CH₂)_(p)CH(OH)—(CH₂)_(q)—; wherein R′is a hydrogen or an alkyl group, and each of p and q is an integer of atleast 0, provided that p+q is an integer of from 1 to
 22. 12. Aminiemulsion according to claim 11 wherein said fluoroalkyl monomer isselected from the group consisting of: F(CF₂)₅CH₂OCOCR═CH₂,F(CF₂)₆CH₂CH₂OCOCR═CH₂, H(CF₂)₆CH₂CH₂OCOCR═CH₂, F(CF₂)₈CH₂CH₂OCOCR═CH₂,i-C₃F₇(CF₂)₅CH₂CH₂OCOCR═CH₂, F(CF₂)₈SO₂N(C₃H₇)CH₂CH₂OCOCR═CH₂,F(CF₂)₈(CH₂)₄OCOCR═CH₂, F(CF₂)₈SO₂N(CH₃)CH₂CH₂OCOCR═CH₂,F(CF₂)₈SO₂N(C₂H₅)CH₂CH₂OCOCR═CH₂, F(CF₂)₈CONHCH₂CH₂OCOCR═CH₂,i-C₃F₇(CF₂)₅(CH₂)₃OCOCR═CH₂, i-C₃F₇(CF₂)₅CH₂CH(OCOCH₃)OCOCR═CH₂,i-C₃F₇(CF₂)₅CH₂CH₂CH(OH)CH₂OCOCR═CH₂, F(CF₂)₉CH₂CH₂OCOCR═CH₂, andF(CF₂)₉CONHCH₂CH₂OCOCR═CH₂; wherein R represents a hydrogen or a methylgroup, and i-C₃F₇ represents a perfluoroisopropyl group [(CF₃)₂CF—]. 13.A miniemulsion according to claim 10 wherein said fluoroalkyl compoundis perfluoroalkylethyl acrylate or perfluoroalkylmethyl acrylate;wherein the alkyl group has about 6 to about 14 carbon atoms.
 14. Aminiemulsion according to claim 10 wherein said ethylenicallyunsaturated monomer is at least one selected from the group consistingof styrenic compounds, ethylenically unsaturated compounds,nitrogen-containing compounds, vinyl chloride, and vinylidene chloride.15. A miniemulsion according to claim 14 wherein said styrenic compoundis at least one selected from the group consisting of styrene, α-methylstyrene, vinyl naphthalene, vinyl toluene, and chloromethyl styrene. 16.A miniemulsion according to claim 14 wherein said ethylenicallyunsaturated compounds is at least one selected from the group consistingof methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate,ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexylmethacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, octylacrylate, octyl methacrylate, isodecyl acrylate, isodecyl methacrylate,lauryl methacrylate, lauryl acrylate, tridecyl acrylate, tridecylmethacrylate, stearyl acrylate, stearyl methacrylate, glycidylmethacrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate,di-octylmaleate, acetoacetoxyethyl methacrylate, acetoacetoxyethylacrylate, acetoacetoxypropyl methacrylate, acetoacetopropryl acrylate,diacetone acrylamide, acrylamide, methacrylamide, hydroxyethylmethacrylate, hydroxyethyl acrylate, allyl methacrylate,tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexylmethacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexylmethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate,isodecyl methacrylate, isodecyl acrylate, 2-methoxy acrylate, 2-methoxymethacrylate, 2-(2-ethoxyethoxy) ethylacrylate, 2-phenoxyethyl acrylate,2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate,caprolactone acrylate, caprolactone methacrylate, polypropyleneglycolmonoacrylate, polypropyleneglycol monomethacrylate,poyethyleneglycol(400) acrylate, polypropyleneglycol(400) methacrylate,benzyl acrylate, benzyl methacrylate, sodium 1-allyloxy-2-hydroylpropylsulfonate, and acrylonitrile.
 17. A miniemulsion according to claim 14wherein said nitrogen containing compound is at least one selected fromthe group consisting of methacrylamide, t-butylaminoethyl methacrylate,dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,N,N-dimethylaminopropyl methacrylamide, 2-t-butylaminoethylmethacrylate, N,N-dimethylaminoethyl acrylate,2-acrylamido-2-methylpropanesulfonic acid,N-(2-methacryloyloxy-ethyl)ethylene urea, methacrylamidoethylethyleneurea.
 18. A miniemulsion according to claim 14 wherein saidethylenically unsaturated monomer is lauryl methacrylate.
 19. Aminiemulsion according to claim 10 wherein said water-dispersiblepolyester is a polyethylene glycol polyester.
 20. An aqueous dispersioncomprising a polymer, at least one water-dispersible polyester, andwater; wherein said polymer comprises repeating units from at least onefluoroalkyl monomer and optionally at least one ethylenicallyunsaturated monomer; wherein said fluoroalkyl monomer is a(meth)acrylate having a Rf group; wherein the Rf group is a group havingat least two hydrogen atoms of an alkyl group substituted by fluorineatoms; wherein the fluoroalkyl monomer is represented by the formulaRf-Q-OCOCR═CH₂; wherein Q is a bivalent organic group, R is hydrogenatom or methyl group; wherein Q is selected from the group consisting of—(CH₂)_(p+q)—; —(CH₂)_(p)CONH(CH₂₎ _(q)—; —(CH₂)OCONH(CH₂)_(q)—;—(CH₂)_(p)SO₂NR′(CH₂)_(q)—; —(CH₂)_(p)NHCONH(CH₂)_(q)—; or—(CH₂)_(p)CHOH—(CH₂)_(q)—; wherein R′ is a hydrogen or an alkyl group,and each of p and q is an integer of at least 0, provided that p+q is aninteger of from 1 to 22; and wherein the amount of water-dispersiblepolyester solids in the aqueous dispersion ranges from 3% to 5% based onthe total weight of said aqueous dispersion.
 21. An aqueous dispersionaccording to claim 20 wherein the carbon number of said Rf group is from2 to about
 20. 22. An aqueous dispersion according to claim 21 whereinthe carbon number of said Rf group is from 6 to
 14. 23. An aqueousdispersion according to claim 20 wherein the number of fluorine atoms insaid Rf group is at least 60%, as represented by [(the number offluorine atoms in the Rf group)/(the number of hydrogen atoms containedin an alkyl group having the same carbon number as the Rfgroup)]×100(%).
 24. An aqueous dispersion according to claim 23 whereinthe number of fluorine atoms in said Rf group is at least 80%, asrepresented by [(the number of fluorine atoms in the Rf group)/(thenumber of hydrogen atoms contained in an alkyl group having the samecarbon number as the Rf group)]×100(%).
 25. An aqueous dispersionaccording to claim 24 wherein said Rf group is a perfluoroalkyl group.26. An aqueous dispersion according to claim 25 wherein the number ofcarbon atoms in said perfluoralkyl group is from 2 to about
 20. 27. Anaqueous dispersion according to claim 21 wherein the fluoroalkyl monomeris represented by the formula: Rf-Q-OCOCR═CH₂; wherein Q is a bivalentorganic group, and R is a hydrogen atom or methyl group.
 28. An aqueousdispersion according to claim 27 wherein Q is selected from the groupconsisting of —(CH₂)_(p+q)—; —(CH₂)_(p)CONH(CH₂)_(q)—;(CH₂)_(p)OCONH(CH₂)_(q)—; —(CH₂)_(p)SO₂NR′(CH₂)_(q)—;(CH₂)_(p)NHCONH(CH₂)_(q)—; or —(CH₂)_(p)CH(OH)—(CH₂)_(q)—; wherein R′ isa hydrogen or an alkyl group, and each of p and q is an integer of atleast 0, provided that p+q is an integer of from 1 to
 22. 29. An aqueousdispersion according to claim 28 wherein Q is selected from the groupconsisting of —(CH₂)_(p+q)—; —(CH₂)_(p)CONH(CH₂)_(q)—; and—(CH₂)_(p)SO₂NR′(CH₂)_(q)—; wherein q is an integer of at least 2; andp+q is from 2 to
 6. 30. An aqueous dispersion according to claim 29wherein Q is (CH₂)_(p+q), and wherein p+q is from 2 to
 6. 31. An aqueousdispersion according to claim 28 wherein said fluoroalkyl monomer isselected from the group consisting of: F(CF₂)₅CH₂OCOCR═CH₂,F(CF₂)₆CH₂CH₂OCOCR═CH₂, H(CF₂)₆CH₂CH₂OCOCR═CH₂, F(CF₂)₈CH₂CH₂OCOCR═CH₂,i-C₃F₇(CF₂)₅CH₂CH₂OCOCR═CH₂, F(CF₂)₈SO₂N(C₃H₇)CH₂CH₂OCOCR═CH₂,F(CF₂)₈(CH₂)₄OCOCR═CH₂, F(CF₂)₈SO₂N(CH₃)CH₂CH₂OCOCR═CH₂,F(CF₂)₈SO₂N(C₂H₅)CH₂CH₂OCOCR═CH₂, F(CF₂)₈CONHCH₂CH₂OCOCR═CH₂,i-C₃F₇(CF₂)₅(CH₂)₃OCOCR═CH₂, i-C₃F₇(CF₂)₅CH₂CH(OCOCH₃)OCOCR═CH₂,i-C₃F₇(CF₂)₅CH₂CH₂CH(OH)CH₂OCOCR═CH₂, F(CF₂)₉CH₂CH₂OCOCR═CH₂, andF(CF₂)₉CONHCH₂CH₂OCOCR═CH₂; wherein R represents a hydrogen or a methylgroup, and i-C₃F₇ represents a perfluoroisopropyl group [(CF₃)₂CF—]. 32.An aqueous dispersion according to claim 27 wherein said fluoroalkylcompound is perfluoroalkylethyl acrylate or perfluoroalkylmethylacrylate; wherein the alkyl group has about 6 to about 14 carbon atoms.33. An aqueous dispersion according to claim 20 wherein saidethylenically unsaturated monomer is at least one selected from thegroup consisting of styrenic compounds, ethylenically unsaturatedcompounds, nitrogen-containing compounds, vinyl chloride, and vinylidenechloride.
 34. An aqueous dispersion according to claim 33 wherein saidstyrenic compound is at least one selected from the group consisting ofstyrene, α-methyl styrene, vinyl naphthalene, vinyl toluene, andchloromethyl styrene.
 35. An aqueous dispersion according to claim 33wherein said ethylenically unsaturated compounds is at least oneselected from the group consisting of methyl acrylate, acrylic acid,methacrylic acid, methyl methacrylate, ethyl acrylate, ethylmethacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate,isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate ethylhexylacrylate, ethylhexyl methacrylate, octyl acrylate, octyl methacrylate,isodecyl acrylate, isodecyl methacrylate, lauryl methacrylate, laurylacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate,stearyl methacrylate, glycidyl methacrylate, alkyl crotonates, vinylacetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethylmethacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropylmethacrylate, acetoacetopropryl acrylate, diacetone acrylamide,acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethylacrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate,tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexylacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethylacrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecylacrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy)ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate,isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate,caprolactone methacrylate, polypropyleneglycol monoacrylate,polypropyleneglycol monomethacrylate, poyethyleneglycol(400) acrylate,polypropyleneglycol(400) methacrylate, benzyl acrylate, benzylmethacrylate sodium 1-allyloxy-2-hydroylpropyl sulfonate, andacrylonitrile.
 36. An aqueous dispersion according to claim 33 whereinsaid nitrogen containing compound is at least one selected from thegroup consisting of methacrylamide, t-butylaminoethyl methacrylate,dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,N,N-dimethylaminopropyl methacrylamide, 2-t-butylaminoethylmethacrylate, N,N-dimethylaminoethyl acrylate,2-acrylamido-2-methylpropanesulfonic acid,N-(2-methacryloyloxy-ethyl)ethylene urea, methacrylamidoethylethyleneurea.
 37. An aqueous dispersion according to claim 33 wherein saidethylenically unsaturated monomer has up to about 18 carbon atoms. 38.An aqueous dispersion according to claim 37 wherein said ethylenicallyunsaturated monomer is lauryl methacrylate.
 39. An aqueous dispersionaccording to claim 20 wherein the amount of fluoroalkyl monomerrepeating units in said polymer ranges from about 50 to about 100 weightpercent based on the total weight of monomer utilized to produce saidpolymer.
 40. An aqueous dispersion according to claim 39 wherein theamount of fluoroalkyl repeating units in said polymer ranges from about60 to about 80 weight percent based on the total weight of monomerutilized to produce said polymer.
 41. An aqueous dispersion according toclaim 20 wherein said water-dispersible polyester is a polyethyleneglycol polyester.
 42. An aqueous dispersion according to claim 20wherein the amount of said water-dispersible polyester solids in theaqueous dispersion ranges from about 1% to about 20% based on the totalweight of said aqueous dispersion.
 43. An aqueous dispersion accordingto claim 20 further comprising at least one compound selected from thegroup consisting of other water repellents and oil repellents,anti-fungus agents, flame retardants, antistatic agents, crease-proofingagents, antimigrants, defoamers, binders, and other antifouling agents.44. A substrate coated with said aqueous dispersion of claim
 20. 45. Asubstrate according to claim 44 wherein said substrate is selected fromthe group consisting of a fiber, yarn, thread, fabric, paper material,and carpet.
 46. A fabric coated with said aqueous dispersion of claim20.